Abstract:Herein, taking inspirations from metalloenzymes, we constructed atomically dispersed manganese sites anchored onto conjugated tri-s-triazine units of graphitic carbon nitride as a bioinspired photocatalyst (Mn 1 /tri-CN) for the oxo-dehydrogenation of N-heterocycles. The primary coordination sphere of atomic Mn-N 2 sites (role i: oxygen activation) as well as the π−π stacking interactions between tri-s-triazine units and substrate mimicking the secondary coordination sphere (role ii: substrate adsorption) syne… Show more
“…Due to the presence of O dopant in Ru 3 O 2 , the H abstraction process proceeds very differently from the reported reaction mechanism, wherein the H atom is usually abstracted one by one. [33][34][35][36] iii) Second H abstraction: the remaining H atom on the C1 group is transferred to HO-O* on terminal Ru atom to form the first H 2 O molecule with an energy decrease of 0.05 eV. iv) First equilibration: as the H 2 O molecule is still adsorbed on the terminal Ru atom, the intramolecular H atom transfers from the second neighboring CH 2 group (C2) to C1 with an energy decrease of 1.09 eV to reach the first equilibration of reaction, generating the 1,4-dihydroquinoline (1,4-DHQ) intermediates.…”
Section: Theoretical Studies Of the Catalytic Originmentioning
Single cluster catalysts (SCCs) consisting of atomically precise metal nanoclusters dispersed on supports represent a new frontier of heterogeneous catalysis. However, the ability to synthesize SCCs with high loading and to precisely introduce non‐metal atoms to further tune their catalytic activity and reaction scope of SCCs have been longstanding challenges. Here, a new interface confinement strategy is developed for the synthesis of a high density of atomically precise Ru oxide nanoclusters (Ru3O2) on reduced graphene oxide (rGO), attributed to the suppression of diffusion‐induced metal cluster aggregation. Ru3O2/rGO exhibits a significantly enhanced activity for oxidative dehydrogenation of 1,2,3,4‐tetrahydroquinoline (THQ) to quinoline with a high yield (≈86%) and selectivity (≈99%), superior to Ru and RuO2 nanoparticles, and homogeneous single/multiple‐site Ru catalysts. In addition, Ru3O2/rGO is also capable of efficiently catalyzing more complex oxidative reactions involving three reactants. The theoretical calculations reveal that the presence of two oxygen atoms in the Ru3O2 motif not only leads to a weak hydrogen bonding interaction between the THQ reactant and the active site, but also dramatically depletes the density of states near the Fermi level, which is attributed to the increased positive valence state of Ru and the enhanced oxidative activity of the Ru3O2 cluster for hydrogen abstraction.
“…Due to the presence of O dopant in Ru 3 O 2 , the H abstraction process proceeds very differently from the reported reaction mechanism, wherein the H atom is usually abstracted one by one. [33][34][35][36] iii) Second H abstraction: the remaining H atom on the C1 group is transferred to HO-O* on terminal Ru atom to form the first H 2 O molecule with an energy decrease of 0.05 eV. iv) First equilibration: as the H 2 O molecule is still adsorbed on the terminal Ru atom, the intramolecular H atom transfers from the second neighboring CH 2 group (C2) to C1 with an energy decrease of 1.09 eV to reach the first equilibration of reaction, generating the 1,4-dihydroquinoline (1,4-DHQ) intermediates.…”
Section: Theoretical Studies Of the Catalytic Originmentioning
Single cluster catalysts (SCCs) consisting of atomically precise metal nanoclusters dispersed on supports represent a new frontier of heterogeneous catalysis. However, the ability to synthesize SCCs with high loading and to precisely introduce non‐metal atoms to further tune their catalytic activity and reaction scope of SCCs have been longstanding challenges. Here, a new interface confinement strategy is developed for the synthesis of a high density of atomically precise Ru oxide nanoclusters (Ru3O2) on reduced graphene oxide (rGO), attributed to the suppression of diffusion‐induced metal cluster aggregation. Ru3O2/rGO exhibits a significantly enhanced activity for oxidative dehydrogenation of 1,2,3,4‐tetrahydroquinoline (THQ) to quinoline with a high yield (≈86%) and selectivity (≈99%), superior to Ru and RuO2 nanoparticles, and homogeneous single/multiple‐site Ru catalysts. In addition, Ru3O2/rGO is also capable of efficiently catalyzing more complex oxidative reactions involving three reactants. The theoretical calculations reveal that the presence of two oxygen atoms in the Ru3O2 motif not only leads to a weak hydrogen bonding interaction between the THQ reactant and the active site, but also dramatically depletes the density of states near the Fermi level, which is attributed to the increased positive valence state of Ru and the enhanced oxidative activity of the Ru3O2 cluster for hydrogen abstraction.
“…Copyright 2020, Wiley‐VCH. (C) Reaction paths and free energy diagrams of CO 2 reduction to CO for Ni‐N 4 ‐C and Ni‐N 3 ‐C. Source : Reproduced with permission 112. Copyright 2021, Wiley‐VCH. (D) Schematic illustration for Zn–CO 2 battery.…”
Section: Applications In Energy Devicesmentioning
confidence: 99%
“…Copyright 2021, Wiley‐VCH. (D) Schematic illustration for Zn–CO 2 battery. Source : Reproduced with permission 112. Copyright 2021, Wiley‐VCH. (E) Faradaic efficiency of Ni‐N 3 ‐C for CO and H 2 during the discharge process under different current densities.…”
Section: Applications In Energy Devicesmentioning
confidence: 99%
“…Copyright 2021, Wiley‐VCH. (E) Faradaic efficiency of Ni‐N 3 ‐C for CO and H 2 during the discharge process under different current densities. Source : Reproduced with permission 112. Copyright 2021, Wiley‐VCH. (F) Population distributions, and (G) free energy profiles of CO 2 RR processes for Ni‐N 3 @C, Ni‐N 3 /GN@C, and Ni‐N 3 /PN@C models.…”
Single-metal-atom catalysts (SMACs) with the merits of maximum atom utilization, peculiar electronic structure, and adjustable coordination environment, have emerged as the rising stars. They are not only regarded as the promising electrocatalysts, but also show unconventionally excellent alkali storage, thus enabling them for energy devices. In this work, we review the up-to-date progress of single metal atom catalysts including the detailed synthetic strategies and all sorts of applications in energy storage and conversion. In addition, we also discuss intrinsic catalytic effects, degradation mechanism, modulation approaches, support structure design, current challenges, and potential development trends. This work may shed light on developing high-performance SMACs using a variety of strategies for catalytic and energy applications.
“…The syntheses of SAs and NCs on g-C 3 N 4 (ref. [114][115][116], porous SiO 2 (ref. 117 and 118) and carbon-based materials [119][120][121][122] have been shown to offer exciting catalytic performance in many reports.…”
This article highlights some recent advances in the electronic and geometric structures of single-atom and nanocluster catalysts, which play an inevitably important role in modern catalysis. The combined use of...
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